Most molecules of chemistry and biology are chiral, leading to mirror image variants, so called enantiomers. However, while the selective chemical synthesis of molecules where the stereogenicity arises from a carbon atom is well-established, enantioselective approaches to nitrogen-stereogenic molecules are much less common,1-3 and in case of acyclic, N-stereogenic amines, even elusive, due to their rapid pyramidal inversion. We describe here the catalytic asymmetric synthesis of stable, acyclic N-stereogenic amines by the addition of enol silanes to nitronium ions that ion pair to a confined chiral anion. In the produced so-called anomeric amines, the commonly observed isomerization is slowed down by two N-oxy-substituents, which hamper nitrogen inversion. The critical stereogenicity creating step challenges previously established stereochemical descriptors of enantiodifferentiation. Computational studies provide additional insight into the origin of the observed stereocontrol. Our work opens up a new avenue to investigate the fascinating and previously underexplored chemistry of enantiopure anomeric amines.